JP4054987B2 - Amino compounds - Google Patents

Amino compounds Download PDF

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Publication number
JP4054987B2
JP4054987B2 JP2003006126A JP2003006126A JP4054987B2 JP 4054987 B2 JP4054987 B2 JP 4054987B2 JP 2003006126 A JP2003006126 A JP 2003006126A JP 2003006126 A JP2003006126 A JP 2003006126A JP 4054987 B2 JP4054987 B2 JP 4054987B2
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Prior art keywords
amino compound
epoxy resin
formula
reaction
styrene
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JP2003006126A
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JP2004217560A (en
Inventor
久征 桑原
雅敏 越後
剛司 小山
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Mitsubishi Gas Chemical Co Inc
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Mitsubishi Gas Chemical Co Inc
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Priority to JP2003006126A priority Critical patent/JP4054987B2/en
Priority to EP03020588A priority patent/EP1403244B1/en
Priority to DE60312088T priority patent/DE60312088T2/en
Priority to US10/669,701 priority patent/US7301053B2/en
Publication of JP2004217560A publication Critical patent/JP2004217560A/en
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  • Epoxy Resins (AREA)

Description

【0001】
【発明の属する技術分野】
本発明はイソホロンジアミンとスチレンとの付加反応により得られるアミノ化合物に関する。このアミノ化合物は自動車用電着塗料、船舶・橋梁・陸海上鉄構築物用重防食塗料、飲料用缶の内面塗装用塗料などの塗料用途、積層板、半導体封止材、絶縁粉体塗料、コイル含浸として家電製品、通信機器、自動車・航空機の制御系などに用いられる電気・電子用途、橋梁の耐震補強、コンクリート構造物のライニング・補強・補修、建築物の床材、上下水道設備のライニング、排水・透水舗装などの土木・建築用途、車両・航空機用などの接着剤用途、航空機、産業資材、スポーツ用品などの複合材料用途、などのきわめて広い分野で利用されているエポキシ樹脂の硬化剤および硬化剤原料として、またフォーム、エラストマー、塗料、接着剤、バインダー、繊維、皮革、床材、防水剤、アスレチック材、シーラント、コーキング、医用材料、繊維処理剤として、衣類、スポーツ用品、生活用品、エレクトロニクス、医療用機器、自動車、運輸機器、土木建築、産業資材分野などの広い分野で利用されているポリウレタン樹脂の鎖延長剤および鎖延長剤原料として利用する事ができる。
【0002】
【従来の技術】
各種ポリアミノ化合物は、エポキシ樹脂硬化剤およびその原料として、またポリウレタン樹脂鎖延長剤およびその原料に用いられていることは広く知られている。イソホロンジアミンを原料とするエポキシ樹脂硬化剤は鎖状脂肪族ポリアミノ化合物、およびそれを原料とするエポキシ樹脂硬化剤と比較して、光沢および平滑性に優れた塗膜を与え、耐水性、耐薬品性に優れた硬化物を与える等の特長を有している(非特許文献1参照)。
【0003】
しかしイソホロンジアミンは、無変性のままでエポキシ樹脂硬化剤として用いられることは稀で、一般には種々の変性を行なって使用されている。代表的な変性方法としては、1.カルボキシル基を有する化合物との反応による変性、2.エポキシ化合物との反応による変性、3.アルデヒド化合物とフェノール化合物とのマンニッヒ反応による変性、4.アクリル化合物とのマイケル付加反応による変性、などが挙げられる。
【0004】
これらの変性を行なうことにより、有害蒸気の低減、硬化時の発熱性の改善、硬化物の接着性、耐水性、耐薬品性が改善される。しかし、その反面、イソホロンジアミンを原料として各種変性を行なったエポキシ樹脂硬化剤は、粘度が高くなることが知られている。一般に、硬化剤は作業性の観点より低粘度であることが望ましい。上記の各反応物は変性物であることから、変性割合を下げることによって、低粘度の反応物を得ることができる。しかし、変性割合を下げると、未反応の原料アミンが多く残存し、得られた反応物はエポキシ樹脂硬化剤として、有害蒸気の低減、硬化時の発熱性の改善、硬化物の接着性、耐水性、耐薬品性の改善効果を十分に得ることは難しい。
【0005】
また、上記の目的を達成し、低粘度のエポキシ樹脂硬化剤とするために、変性割合を増加させて、得られた反応物を溶剤で希釈してエポキシ樹脂硬化剤とする方法が用いられている。しかし、近年エポキシ樹脂に使用される硬化剤は、地球環境の汚染防止の観点から、溶剤を使用しない傾向が強まってきており、無用剤系のエポキシ樹脂硬化剤が求められている。
【0006】
また、エポキシ樹脂硬化剤として、メタキシレンジアミン等を変性したアミノ化合物が紹介されており、該アミノ化合物は、比較的低粘度であることが開示されている(特許文献1参照)
【0007】
【非特許文献1】
垣内弘編著 「エポキシ樹脂硬化剤の新展開」 (株)CMC、1994年5月31日 41−49頁
【特許文献1】
特開2002−161076号公報(3−5頁)
【0008】
【発明が解決しようとする課題】
本発明は、低粘度でありながら未反応ポリアミン含有量が低く、エポキシ樹脂硬化剤として使用した際に、良好な硬化物性能を与えるアミノ化合物を提供することを目的とする。
【0009】
【課題を解決するための手段】
本発明者らは、鋭意検討した結果、強塩基触媒下でイソホロンジアミンと、スチレンとの付加反応により新規アミノ化合物が得られること、得られたアミノ化合物を含有する組成物は、エポキシ樹脂硬化剤として、良好な硬化物性能を与えることを見出して本発明に至った。
【0010】
すなわち、本発明は(1)式で示されるアミノ化合物、(2)式で示されるアミノ化合物及び(3)式で示されるアミノ化合物、並びに(1)式で示されるアミノ化合物、(2)式で示されるアミノ化合物及び(3)式で示されるアミノ化合物から選ばれる少なくとも1種のアミノ化合物を15重量%以上含有するエポキシ樹脂硬化剤に関するものである。
【化4】

Figure 0004054987
【化5】
Figure 0004054987
【化6】
Figure 0004054987
【0011】
【発明の実施の形態】
本発明のアミノ化合物は、イソホロンジアミンとスチレンとの付加反応により得られるアミノ化合物である。
【0012】
本発明は、また、イソホロンジアミンのメチレンアミノ基にフェネチル基が結合した(1)式に示される化合物、イソホロンジアミンのアミノ基にフェネチル基が結合した(2)式に示される化合物、または、イソホロンジアミンのメチレンアミノ基とアミノ基にそれぞれフェネチル基が結合した(3)式に示される化合物である。これらは、イソホロンジアミンとスチレンとの付加反応により得られる。
【0013】
【化7】
Figure 0004054987
【0014】
【化8】
Figure 0004054987
【0015】
【化9】
Figure 0004054987
【0016】
本発明において、イソホロンジアミンとスチレンから上記アミノ化合物を合成する際には、強塩基性を呈する触媒を使用することが好ましい。例えば、アルカリ金属、アルカリ金属アミド、アルキル化アルカリ金属などがあるが、好ましくはアルカリ金属アミド(一般式MNRR’:Mはアルカリ金属、Nは窒素、RおよびR’は各々独立して水素またはアルキル基である)であり、特にリチウムアミド(LiNH)が好ましい。触媒の使用量は、原料の種類や反応比率、反応温度等の条件により異なるが、通常は原料中に0.05〜5重量%であり、好ましくは0.1〜3重量%である。
【0017】
本発明のアミノ化合物を合成する際の反応温度は、通常50〜130℃であり、これより反応温度が低い場合にはイソホロンジアミンとスチレンの反応速度が遅く、逆に反応温度が高い場合には、副生成物としてスチレンの重合物が生成することから、反応比率、触媒の種類と量に応じて反応温度を選択することが望ましい。
【0018】
本発明のアミノ化合物を合成する際に触媒として使用するアルカリ金属アミド等の強塩基触媒は、空気中の水や二酸化炭素と容易に反応するため、反応は窒素、ヘリウム、アルゴンなどの不活性ガス雰囲気中で行い、水分や二酸化炭素の影響を除外することが必要である。
【0019】
本発明のイソホロンジアミンとスチレンの反応は発熱反応であり、反応温度を一定に保つためには発熱によって生じる温度上昇を制御する必要がある。また、スチレンの重合を抑制するために、スチレンは一定の反応温度の範囲内で滴下により添加することが望ましい。スチレンの滴下に要する時間は反応比率、触媒量に応じて選択することが望ましい。
【0020】
反応速度は、イソホロンジアミン及びスチレンの反応比率、反応温度、触媒の種類と量に大きく支配されるため、反応時間は条件により設定されるべきであるが、反応中に反応液のサンプリングを行ない、ガスクロマトグラフィーや液体クロマトグラフィー等で原料であるスチレンの定量を行ない、未反応のスチレンが1重量%以下になるまでを反応時間とすることが望ましい。
【0021】
反応終了後に得られる反応液中には、反応により生成したアミノ化合物と触媒のアルカリ金属アミドが含まれる。触媒のアルカリ金属アミドは、ろ過により除去可能である。ろ過の場合は、塩酸、塩化水素ガス、酢酸などの酸、メタノール、エタノール等のアルコール、あるいは水等を加えてアルカリ金属アミドを除去容易な塩に変えてからろ過することが可能である。例えば水を用いた場合には、アルカリ金属アミドが水酸化物となり、ろ過が容易となる。
【0022】
上記の反応により得られたアミノ化合物は、25℃における粘度が35〜3000mPa・sの淡黄色透明の液体である。
【0023】
触媒のアルカリ金属アミドが除去された反応液中には、(1)、(2)式で示されるイソホロンジアミン1分子中の1級アミンに対してスチレン1分子が付加した1対1付加体、(3)式で示されるイソホロンジアミン1分子中の2つの1級アミンそれぞれにスチレンが1分子付加した1対2付加体、その他、イソホロンジアミン1分子の1つの1級アミンにスチレン2分子が付加し、もう1つの1級アミンにはスチレン1分子が付加した1対3付加体、イソホロンジアミン1分子中の2つの1級アミンにスチレン4が2分子づつ付加した物1対4付加体などのアミノ化合物と、未反応のイソホロンジアミンが含まれる。アミノ化合物中の各付加物の含有率は、イソホロンジアミンとスチレンとの反応比率に支配され、スチレンの比率が高いほど付加分子数が大きい付加体の割合が多くなる。
【0024】
本発明によって得られるアミノ化合物は、エポキシ樹脂やイソシアネート等との反応性を有し、エポキシ樹脂硬化剤およびウレタン樹脂の鎖延長剤として有用である。さらには紙力増強剤、ゴム用薬品、清缶剤、スラグ防止剤、界面活性剤、乳化剤、染料、顔料、染色助剤、繊維用油剤、化粧品、防皺加工剤、キレート剤、浮遊選鉱剤、洗剤、チクソ剤、pH調整剤、殺虫剤、除草剤、農薬安定剤、飼料添加剤、触媒、重合促進剤、重合防止剤、安定剤、イオン交換樹脂、ガス吸収剤、抗酸化剤、防蝕剤、防錆剤、殺菌剤、抗菌剤、不凍液、潤滑油、滑剤、医薬中間体、ポリアミド、溶剤、写真薬など様々な分野で幅広く利用することができる。
【0025】
本発明のアミノ化合物をエポキシ樹脂硬化剤として用いるには、(1)、(2)および(3)式で示されるアミノ化合物の含有量が15重量%以上であることが好ましい。
【0026】
本発明のアミノ化合物をエポキシ樹脂硬化剤として使用する場合には、単独で使用してもよいし、他のポリアミン系エポキシ樹脂硬化剤と混合して使用してもよい。この場合の混合量は、本発明のアミノ化合物の特徴が損なわれない範囲であれば特に限定されるものではないが、5〜80重量%の範囲が好ましい。
【0027】
本発明のアミノ化合物は、ポリアミン系エポキシ樹脂硬化剤のアミン原料として、さらに変性して使用することもできる。この場合は、スチレンによる変性モル数は、得られる化合物が活性水素を持つアミノ基を含有し、本発明のアミノ化合物の特徴が損なわれないような割合であれば特に限定されない。また、変性方法は通常のポリアミン系硬化剤に利用されている方法でよく、特に限定されるものではない。
【0028】
【実施例】
以下に、本発明を実施例によって具体的に説明するが、本発明はこれによって限定されるものではない。なお、アミノ化合物の分析、およびエポキシ樹脂塗膜性能の評価は、以下の方法にて行なった。
<アミノ化合物の分析>
(1)ガスクロマトグラム−質量(GC−MS)分析法
GC装置:島津製作所(株)製 GC−17A
MS装置:島津製作所(株)製 QP5050A
カラム:J&W社製 DB−1(長さ15m、内径0.25mm、Film厚0.1μm)
カラムオーブン温度:120℃/10分+10℃/分 昇温+300℃/40分<エポキシ樹脂塗膜性能評価>
エポキシ樹脂組成物を、23℃、50%RHの条件下で、鋼板に200μmの厚みで塗装した。
外観:7日後の塗膜外観(光沢、透明性、平滑性)を目視で評価し、乾燥性はは指触により評価した。
耐水性:1、4および7日後の塗膜上に水滴を滴下し、1日放置後の塗膜の変化を目視にて評価した。
耐薬品性、7日硬化後の塗装鋼板を各薬品に7日間23℃で浸漬し、塗膜の変化を目視により評価した。
耐塩水噴霧性:JIS K 5400に準拠し、7日後塩水噴霧後の塗膜の変化を目視により評価した。
評価方法:4段階で評価
◎:優秀、 ○:良好 △:やや不良 ×:不良
【0029】
実施例1
撹拌装置、温度計、窒素導入管、滴下漏斗、およびコンデンサーを備えた内容積2リットルの丸底フラスコに、イソホロンジアミン(IPDA;デグッサ社製)681.2g(4.0モル)とリチウムアミド(メルク(株)製試薬)3.3g(0.14モル)を仕込み、窒素気流下、撹拌しながら80℃に昇温した。昇温後スチレン(和光純薬工業(株)製、試薬特級)416.8g(4.0モル)を2.5時間かけて滴下した。滴下後1時間80℃に保ったのち、室温に冷却した。室温に冷却後、仕込んだリチウムアミドの10倍モル量の水25.2g(1.4モル)を加え攪拌した。その後、濾過して沈殿物を分離後、残存する水を減圧蒸留にて除去し、再度濾過して、アミノ化合物A、1032.7gを得た。アミノ化合物Aの粘度は90mPa・s/25℃であり、未反応スチレン0.03重量%、未反応イソホロンジアミン(IPDA)は14.6重量%だった。
【0030】
得られたアミノ化合物をGC−MS分析した結果、未反応IPDAの他に、5つのピークが観測された。5つのピークを保持時間の順にピークa、b、c、d、eとすると、ピーク面積比は、IPDA:11.2%、ピークa:9.2%、ピークb:33.5%、ピークc:11.1%、ピークd:9.5%、ピークe:25.6%であった。(図1参照)
【0031】
a、b、c、d、eの各ピークのGC−MS分析結果から、ピークaは、183m/z(M−91)の他、152m/z、134m/z、124m/z、105m/zが存在することから、(1)式のトランス体であることが確認された。
【0032】
ピークbは、183m/z(M−91)の他、166m/z、134m/z、124m/z、105m/zが存在することから、(1)式のシス体であることが確認された。
【0033】
ピークcには、183m/z(M−91)の他、166m/z、105m/zの他に、30m/z(CH=NH )が存在することから、(2)式であることが確認された。
【0034】
ピークd、eには、287m/z(M−91)の他、258m/z(M−120)、166m/z、154m/z、134m/z、105m/zが存在することから、(3)式の化合物であることが確認された。
【0035】
またピークd、eのGC−MS分析結果より、ピークdの287m/z(M−91)、258m/z(M−120)は、同等のピーク強度で検出された。また、ピークeでは、287m/z(M−91)のピーク強度が強く、258m/z(M−120)のピーク強度は弱かった。(3)式で示される化合物は、(4)式と(5)式で示される異性体を持つと推測される。(4)式で示される化合物は1,3−アキシアル位相互作用により、シクロヘキサン環に結合したアミノ基の脱離が容易になる。この結果より、ピークdは(4)式で示される化合物、ピークeは(5)式に示される化合物であると同定された。
【0036】
【化10】
Figure 0004054987
Figure 0004054987
(ただし、Rはフェネチル基を示す。)
【0037】
【化11】
Figure 0004054987
Figure 0004054987
(ただし、Rはフェネチル基を示す。)
【0038】
実施例1で得られたアミノ化合物をエポキシ樹脂硬化剤として使用して、ビスフェノールA型液状エポキシ樹脂(ジャパンエポキシレジン(株)製、商品名:エピコート828、エポキシ当量:190g/eq)と表1に示す割合で配合し、エポキシ樹脂硬化塗膜を作成して、23℃、50%RHの条件下で硬化させて性能評価を行なった。評価結果を表1に示した。
【0039】
比較例1
実施例1と同様のフラスコにIPDA681.2g(4.0モル)を仕込み、窒素気流下、攪拌しながら80℃に昇温した。80℃に保ちながら、ブチルグリシジルエーテル(日本油脂(株)製、商品名:ニッサンエピオールB、エポキシ当量:130g/eq、以下BGEと記載)520.0g(4.0モル)を2時間かけて滴下した。滴下終了後、100℃に昇温して2時間反応を行い、IPDAのBGE付加物1181.4gを得た。IPDAのBGE付加物の粘度は3400mPa・s/25℃、未反応IPDA量は15.1重量%、活性水素当量は100であった。
【0040】
比較例1で得られたIPDAのBGE付加物をエポキシ樹脂硬化剤として使用した以外は、実施例1と同様の方法でエポキシ樹脂硬化塗膜を作成して評価を行なった。評価結果を表1に示した。
【0041】
【表1】
Figure 0004054987
【0042】
【発明の効果】
以上の実施例から明らかなように、本発明のアミノ化合物は、低粘度でありながら未反応ポリアミン含有量が比較的低く、エポキシ樹脂硬化剤として使用した際に良好な硬化物性能を与える他、様々な分野で幅広く利用することができる。
【0043】
【図面の簡単な説明】
【図1】 実施例1にて合成したアミノ化合物AのGC−MSチャート[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an amino compound obtained by addition reaction of isophoronediamine and styrene. This amino compound is used in electrodeposition coatings for automobiles, heavy duty anti-corrosion coatings for ships, bridges, land and sea iron structures, coatings for interior coatings of beverage cans, laminates, semiconductor encapsulants, insulating powder coatings, coils Electrical and electronic applications used in home appliances, communication equipment, automobile / aircraft control systems as impregnation, seismic reinforcement of bridges, lining, reinforcement and repair of concrete structures, flooring of buildings, lining of water and sewage equipment, Epoxy resin curing agents used in a wide range of fields such as civil engineering and construction applications such as drainage and permeable pavement, adhesive applications for vehicles and aircraft, composite materials applications such as aircraft, industrial materials and sports equipment, and As raw material for hardeners, foam, elastomer, paint, adhesive, binder, fiber, leather, flooring, waterproofing agent, athletic material, sealant, caulking, medical Polyurethane resin chain extenders and chain extenders used in a wide range of applications such as clothing, sporting goods, household goods, electronics, medical equipment, automobiles, transportation equipment, civil engineering, and industrial materials. Can be used as an agent raw material.
[0002]
[Prior art]
It is widely known that various polyamino compounds are used as an epoxy resin curing agent and its raw material, and as a polyurethane resin chain extender and its raw material. Epoxy resin curing agent using isophorone diamine as a raw material gives a coating film with excellent gloss and smoothness compared to chain aliphatic polyamino compound and epoxy resin curing agent using it as a raw material. It has features such as giving a cured product having excellent properties (see Non-Patent Document 1).
[0003]
However, isophorone diamine is rarely used as an epoxy resin curing agent in its unmodified form, and is generally used after various modifications. Typical denaturation methods include: 1. Modification by reaction with a compound having a carboxyl group 2. Modification by reaction with an epoxy compound. 3. Modification by Mannich reaction between an aldehyde compound and a phenol compound. Modification by Michael addition reaction with an acrylic compound.
[0004]
By performing these modifications, the harmful vapor is reduced, the heat generation at the time of curing is improved, the adhesion of the cured product, the water resistance, and the chemical resistance are improved. On the other hand, it is known that an epoxy resin curing agent that has been subjected to various modifications using isophoronediamine as a raw material has a high viscosity. Generally, it is desirable that the curing agent has a low viscosity from the viewpoint of workability. Since each of the above reactants is a modified product, a low-viscosity reactant can be obtained by reducing the modification ratio. However, when the modification ratio is lowered, a large amount of unreacted raw material amine remains, and the obtained reaction product is an epoxy resin curing agent, reducing harmful vapor, improving heat generation during curing, adhesion of cured product, water resistance It is difficult to obtain a sufficient improvement effect on chemical properties and chemical resistance.
[0005]
Further, in order to achieve the above-mentioned object and to obtain a low viscosity epoxy resin curing agent, a method of increasing the modification ratio and diluting the obtained reaction product with a solvent to obtain an epoxy resin curing agent is used. Yes. However, in recent years, curing agents used for epoxy resins are increasingly used without solvents from the viewpoint of preventing pollution of the global environment, and useless epoxy resin curing agents are required.
[0006]
Also, amino compounds obtained by modifying metaxylenediamine or the like have been introduced as epoxy resin curing agents, and it is disclosed that the amino compounds have a relatively low viscosity (see Patent Document 1).
[0007]
[Non-Patent Document 1]
Edited by Hiroshi Kakiuchi "New development of epoxy resin curing agent" CMC Co., Ltd., May 31, 1994, pp. 41-49 [Patent Document 1]
JP 2002-161076 A (page 3-5)
[0008]
[Problems to be solved by the invention]
It is an object of the present invention to provide an amino compound that has a low viscosity but has a low unreacted polyamine content, and gives good cured product performance when used as an epoxy resin curing agent.
[0009]
[Means for Solving the Problems]
As a result of intensive studies, the present inventors have found that a novel amino compound can be obtained by addition reaction of isophoronediamine and styrene under a strong base catalyst, and the composition containing the obtained amino compound is an epoxy resin curing agent. As a result, the present invention was found to give good cured product performance.
[0010]
That is, the present invention relates to an amino compound represented by formula (1), an amino compound represented by formula (2) and an amino compound represented by formula (3), an amino compound represented by formula (1), and formula (2) And an epoxy resin curing agent containing 15% by weight or more of at least one amino compound selected from the group consisting of the amino compound represented by formula (3) and the amino compound represented by formula (3) .
[Formula 4]
Figure 0004054987
[Chemical formula 5]
Figure 0004054987
[Chemical 6]
Figure 0004054987
[0011]
DETAILED DESCRIPTION OF THE INVENTION
The amino compound of the present invention is an amino compound obtained by addition reaction of isophoronediamine and styrene.
[0012]
The present invention also provides a compound represented by the formula (1) in which a phenethyl group is bonded to the methyleneamino group of isophoronediamine, a compound represented by the formula (2) in which a phenethyl group is bonded to the amino group of isophoronediamine, or isophorone. It is a compound represented by the formula (3) in which a phenethyl group is bonded to each of a methyleneamino group and an amino group of diamine. These are obtained by the addition reaction of isophoronediamine and styrene.
[0013]
[Chemical 7]
Figure 0004054987
[0014]
[Chemical 8]
Figure 0004054987
[0015]
[Chemical 9]
Figure 0004054987
[0016]
In the present invention, when synthesizing the amino compound from isophoronediamine and styrene, it is preferable to use a catalyst exhibiting strong basicity. For example, there are alkali metals, alkali metal amides, alkylated alkali metals, etc., preferably alkali metal amides (general formula MNRR ′: M is an alkali metal, N is nitrogen, R and R ′ are each independently hydrogen or alkyl A lithium amide (LiNH 2 ). The amount of the catalyst used varies depending on the type of raw material, reaction ratio, reaction temperature, and the like, but is usually 0.05 to 5% by weight, preferably 0.1 to 3% by weight in the raw material.
[0017]
The reaction temperature at the time of synthesizing the amino compound of the present invention is usually 50 to 130 ° C. When the reaction temperature is lower than this, the reaction rate of isophoronediamine and styrene is slow, and conversely when the reaction temperature is high. Since a styrene polymer is produced as a by-product, it is desirable to select the reaction temperature according to the reaction ratio and the type and amount of the catalyst.
[0018]
A strong base catalyst such as an alkali metal amide used as a catalyst when synthesizing the amino compound of the present invention easily reacts with water or carbon dioxide in the air, so the reaction is an inert gas such as nitrogen, helium or argon. It is necessary to perform in an atmosphere and exclude the influence of moisture and carbon dioxide.
[0019]
The reaction between isophoronediamine and styrene of the present invention is an exothermic reaction, and in order to keep the reaction temperature constant, it is necessary to control the temperature rise caused by the exotherm. Moreover, in order to suppress the polymerization of styrene, it is desirable to add styrene dropwise within a certain reaction temperature range. The time required for dropping styrene is preferably selected according to the reaction ratio and the amount of catalyst.
[0020]
Since the reaction rate is largely controlled by the reaction ratio of isophoronediamine and styrene, reaction temperature, and the type and amount of the catalyst, the reaction time should be set according to the conditions, but the reaction solution is sampled during the reaction, It is desirable to determine the amount of styrene as a raw material by gas chromatography, liquid chromatography or the like, and to set the reaction time until the amount of unreacted styrene becomes 1% by weight or less.
[0021]
The reaction solution obtained after completion of the reaction contains the amino compound produced by the reaction and the alkali metal amide of the catalyst. The alkali metal amide of the catalyst can be removed by filtration. In the case of filtration, it is possible to perform filtration after adding an acid such as hydrochloric acid, hydrogen chloride gas, acetic acid, alcohol such as methanol or ethanol, or water to change the alkali metal amide to a salt that can be easily removed. For example, when water is used, the alkali metal amide becomes a hydroxide, which facilitates filtration.
[0022]
The amino compound obtained by the above reaction is a light yellow transparent liquid having a viscosity at 25 ° C. of 35 to 3000 mPa · s.
[0023]
In the reaction solution from which the alkali metal amide of the catalyst has been removed, a one-to-one adduct in which one molecule of styrene is added to a primary amine in one molecule of isophoronediamine represented by formulas (1) and (2), (3) One-to-two adduct in which one molecule of styrene is added to each of two primary amines in one molecule of isophoronediamine represented by the formula, and two molecules of styrene are added to one primary amine in one molecule of isophoronediamine. The other primary amine is a one-to-three adduct in which one molecule of styrene is added, and the one-to-four adduct in which two molecules of styrene 4 are added to two primary amines in one molecule of isophoronediamine. An amino compound and unreacted isophoronediamine are included. The content of each adduct in the amino compound is governed by the reaction ratio between isophoronediamine and styrene, and the higher the ratio of styrene, the greater the ratio of adducts with a larger number of added molecules.
[0024]
The amino compound obtained by the present invention has reactivity with an epoxy resin, isocyanate and the like, and is useful as a chain extender for epoxy resin curing agents and urethane resins. In addition, paper strength enhancers, rubber chemicals, cleansing agents, anti-slag agents, surfactants, emulsifiers, dyes, pigments, dyeing aids, textile oils, cosmetics, antifungal agents, chelating agents, flotation agents , Detergent, thixotropic agent, pH adjuster, insecticide, herbicide, agrochemical stabilizer, feed additive, catalyst, polymerization accelerator, polymerization inhibitor, stabilizer, ion exchange resin, gas absorbent, antioxidant, anticorrosion It can be widely used in various fields such as agents, rust preventives, bactericides, antibacterial agents, antifreeze solutions, lubricants, lubricants, pharmaceutical intermediates, polyamides, solvents, and photographic drugs.
[0025]
In order to use the amino compound of the present invention as an epoxy resin curing agent, the content of the amino compound represented by the formulas (1), (2) and (3) is preferably 15% by weight or more.
[0026]
When the amino compound of the present invention is used as an epoxy resin curing agent, it may be used alone or in combination with other polyamine epoxy resin curing agents. The mixing amount in this case is not particularly limited as long as the characteristics of the amino compound of the present invention are not impaired, but a range of 5 to 80% by weight is preferable.
[0027]
The amino compound of the present invention can be further modified and used as an amine raw material for a polyamine epoxy resin curing agent. In this case, the number of moles modified with styrene is not particularly limited as long as the resulting compound contains an amino group having active hydrogen and the characteristics of the amino compound of the present invention are not impaired. Further, the modification method may be a method used for a normal polyamine-based curing agent, and is not particularly limited.
[0028]
【Example】
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. In addition, the analysis of an amino compound and evaluation of the epoxy resin coating film performance were performed by the following methods.
<Analysis of amino compounds>
(1) Gas chromatogram-mass (GC-MS) analysis GC apparatus: GC-17A manufactured by Shimadzu Corporation
MS device: QP5050A manufactured by Shimadzu Corporation
Column: DB-1 manufactured by J & W (length 15 m, inner diameter 0.25 mm, film thickness 0.1 μm)
Column oven temperature: 120 ° C./10 minutes + 10 ° C./minute Temperature increase + 300 ° C./40 minutes <Epoxy resin coating film performance evaluation>
The epoxy resin composition was applied to a steel plate with a thickness of 200 μm under the conditions of 23 ° C. and 50% RH.
Appearance: The appearance (gloss, transparency, smoothness) of the coating film after 7 days was visually evaluated, and the drying property was evaluated by touch.
Water resistance: A drop of water was dropped on the coating film after 1, 4 and 7 days, and the change of the coating film after standing for 1 day was visually evaluated.
Chemical resistance, 7 days-hardened coated steel sheet was immersed in each chemical for 7 days at 23 ° C., and changes in the coating film were visually evaluated.
Salt spray resistance: Based on JIS K 5400, the change of the coating film after 7 days after salt spray was visually evaluated.
Evaluation method: Evaluation in 4 stages ◎: Excellent, ○: Good △: Slightly poor ×: Poor [0029]
Example 1
In a 2 liter round bottom flask equipped with a stirrer, thermometer, nitrogen inlet tube, dropping funnel, and condenser, 681.2 g (4.0 mol) of isophoronediamine (IPDA; manufactured by Degussa) and lithium amide ( Merck Co., Ltd. reagent) (3.3 g, 0.14 mol) was charged, and the mixture was heated to 80 ° C. with stirring in a nitrogen stream. After the temperature increase, 416.8 g (4.0 mol) of styrene (manufactured by Wako Pure Chemical Industries, Ltd., reagent grade) was added dropwise over 2.5 hours. After dropping, the temperature was kept at 80 ° C. for 1 hour, and then cooled to room temperature. After cooling to room temperature, 25.2 g (1.4 mol) of water in a 10-fold molar amount of the charged lithium amide was added and stirred. Then, after filtering and isolate | separating a deposit, the remaining water was removed by vacuum distillation and it filtered again, and amino compound A and 1032.7g were obtained. The viscosity of the amino compound A was 90 mPa · s / 25 ° C., 0.03% by weight of unreacted styrene, and 14.6% by weight of unreacted isophoronediamine (IPDA).
[0030]
As a result of GC-MS analysis of the resulting amino compound, 5 peaks were observed in addition to unreacted IPDA. Assuming that the five peaks are peaks a, b, c, d, and e in order of retention time, the peak area ratio is IPDA: 11.2%, peak a: 9.2%, peak b: 33.5%, peak c: 11.1%, peak d: 9.5%, peak e: 25.6%. (See Figure 1)
[0031]
From the results of GC-MS analysis of each peak of a, b, c, d, e, peak a is 183 m / z (M-91), 152 m / z, 134 m / z, 124 m / z, 105 m / z. Therefore, it was confirmed to be a trans isomer of the formula (1).
[0032]
In addition to 183 m / z (M-91), peak b has 166 m / z, 134 m / z, 124 m / z, and 105 m / z, and thus was confirmed to be a cis isomer of formula (1). .
[0033]
In addition to 183 m / z (M-91) and 166 m / z and 105 m / z, 30 m / z (CH 2 = NH 2 + ) is present in peak c, so that the formula (2) is satisfied. It was confirmed.
[0034]
Peaks d and e include 287 m / z (M-91), 258 m / z (M-120), 166 m / z, 154 m / z, 134 m / z, and 105 m / z. ) Was confirmed to be the compound of formula.
[0035]
Further, from the results of GC-MS analysis of peaks d and e, 287 m / z (M-91) and 258 m / z (M-120) of peak d were detected with the same peak intensity. Moreover, in the peak e, the peak intensity of 287 m / z (M-91) was strong, and the peak intensity of 258 m / z (M-120) was weak. The compound represented by the formula (3) is presumed to have isomers represented by the formulas (4) and (5). In the compound represented by the formula (4), elimination of the amino group bonded to the cyclohexane ring is facilitated by the 1,3-axial interaction. From this result, peak d was identified as a compound represented by formula (4), and peak e was identified as a compound represented by formula (5).
[0036]
[Chemical Formula 10]
Figure 0004054987
Figure 0004054987
(However, R represents a phenethyl group.)
[0037]
Embedded image
Figure 0004054987
Figure 0004054987
(However, R represents a phenethyl group.)
[0038]
Using the amino compound obtained in Example 1 as an epoxy resin curing agent, bisphenol A type liquid epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., trade name: Epicoat 828, epoxy equivalent: 190 g / eq) and Table 1 An epoxy resin cured coating film was prepared at a ratio shown in FIG. 5 and cured under conditions of 23 ° C. and 50% RH for performance evaluation. The evaluation results are shown in Table 1.
[0039]
Comparative Example 1
681.2 g (4.0 mol) of IPDA was charged into the same flask as in Example 1, and the temperature was raised to 80 ° C. with stirring in a nitrogen stream. While maintaining the temperature at 80 ° C., 520.0 g (4.0 mol) of butyl glycidyl ether (manufactured by NOF Corporation, trade name: Nissan Epiol B, epoxy equivalent: 130 g / eq, hereinafter referred to as BGE) over 2 hours And dripped. After completion of the dropwise addition, the temperature was raised to 100 ° C. and the reaction was carried out for 2 hours to obtain 1181.4 g of IPDA BGE adduct. The viscosity of the BDA adduct of IPDA was 3400 mPa · s / 25 ° C., the amount of unreacted IPDA was 15.1% by weight, and the active hydrogen equivalent was 100.
[0040]
An epoxy resin cured coating film was prepared and evaluated in the same manner as in Example 1 except that the IPDA BGE adduct obtained in Comparative Example 1 was used as an epoxy resin curing agent. The evaluation results are shown in Table 1.
[0041]
[Table 1]
Figure 0004054987
[0042]
【The invention's effect】
As is clear from the above examples, the amino compound of the present invention has a low viscosity and a relatively low content of unreacted polyamine, and gives good cured product performance when used as an epoxy resin curing agent, It can be widely used in various fields.
[0043]
[Brief description of the drawings]
1 is a GC-MS chart of amino compound A synthesized in Example 1. FIG.

Claims (5)

(1)式で示されるアミノ化合物。
Figure 0004054987
(1) An amino compound represented by the formula:
Figure 0004054987
(2)式で示されるアミノ化合物。
Figure 0004054987
(2) An amino compound represented by the formula:
Figure 0004054987
(3)式で示されるアミノ化合物。
Figure 0004054987
(3) An amino compound represented by the formula:
Figure 0004054987
(1)式で示されるアミノ化合物、(2)式で示されるアミノ化合物及び(3)式で示されるアミノ化合物から選ばれる少なくとも1種のアミノ化合物を15重量%以上含有するエポキシ樹脂硬化剤。An epoxy resin curing agent containing at least 15% by weight of an amino compound represented by the formula (1), an amino compound represented by the formula (2) and an amino compound represented by the formula (3). 前記アミノ化合物が、イソホロンジアミンとスチレンとの付加反応により得られたものである請求項4に記載のエポキシ樹脂硬化剤。The epoxy resin curing agent according to claim 4, wherein the amino compound is obtained by an addition reaction between isophoronediamine and styrene.
JP2003006126A 2002-09-26 2003-01-14 Amino compounds Expired - Lifetime JP4054987B2 (en)

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